resin composition

Abstract

The present invention provides a resin composition that can simultaneously achieve suppression of warping, improved filling of gaps and spaces between electrodes, and improved adhesion. [Solution] A resin composition comprising (A1) an epoxy resin represented by the following formula (a-3), (A2) a liquid epoxy resin having an aromatic skeleton, (B) a curing accelerator, and (C) an inorganic filler, wherein the mass ratio of component (A1) to component (A2) [(A1) component / (A2) component] is 0.1 to 3.5. TIFF2026052333000010.tif21170 (In the formula, each Ar ring independently represents an aromatic carbon ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms; X represents an alkylene group having 1 to 20 carbon atoms; Y independently represents an alkylene group having 1 to 10 carbon atoms; m1 and m2 independently represent integers from 0 to 20, at least one of m1 and m2 is 1 or more; and * represents a bond.)

Description

[Technical Field]

[0001] This invention relates to a resin composition. Furthermore, it relates to a cured product, a printed circuit board, a semiconductor chip package, a semiconductor device, and a method for manufacturing a printed circuit board and a method for manufacturing a semiconductor chip package using the resin composition. [Background technology]

[0002] In recent years, the demand for high-performance electronic devices such as smartphones and tablet devices has increased, and consequently, there is a growing need for even higher performance encapsulating and insulating materials for semiconductor chips and other components used in these small electronic devices (Patent Document 1). Such encapsulating and insulating materials are known to be formed by curing resin compositions. For example, Patent Document 2 describes the use of a liquid epoxy resin composition as an encapsulating material, and a glycidylamine-type epoxy resin is used as the epoxy resin.

[0003] Furthermore, as a method for manufacturing semiconductor chip packages, the mold underfill (MUF) method, which simultaneously fills the narrow gap between the semiconductor chip and the substrate (circuit board) for the semiconductor chip package and completely encapsulates the semiconductor chip using a sealing resin material, is expected to contribute to miniaturization and cost reduction. For example, Patent Document 3 describes using a multilayer sheet having a layer made of a resin composition as the mold underfill sealing material, and states that the resin composition includes biphenyl-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, naphthalene-type epoxy resin, etc. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2022 / 270536 [Patent Document 2] Japanese Patent Application Publication No. 11-255864

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, according to the study by the present inventors, when using a conventional mold underfill encapsulation material, it has been found that it is difficult to simultaneously achieve characteristics such as warpage suppression, filling property into gaps and gaps between electrodes, and adhesion.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition capable of simultaneously achieving warpage suppression, improvement in filling property into gaps and gaps between electrodes, and improvement in adhesion.

Means for Solving the Problems

[0007] As a result of intensive studies by the present inventors, by using a resin composition containing an epoxy resin represented by a specific structure, a liquid epoxy resin having an aromatic skeleton, a curing accelerator, and an inorganic filler, and the mass ratio of two types of epoxy resins being within a specific range, it has been found that the above problems can be solved, and the present invention has been completed.

[0008] That is, the present invention includes the following contents. [1] A resin composition containing: (A1) an epoxy resin represented by the following formula (a-3), (A2) a liquid epoxy resin having an aromatic skeleton, (B) a curing accelerator, and (C) an inorganic filler, where the mass ratio [(A1) component / (A2) component] of the (A1) component to the (A2) component is 0.1 to 3.5.

Chemical formula

[10] The resin composition according to any one of [1] to [9], wherein the total content of component (A1) and component (A2) is 5 to 50% by mass when the nonvolatile components of the resin composition are taken as 100% by mass.

[11] The resin composition according to any one of [1] to

[10] , wherein the content of component (A1) is 2 to 30% by mass when the nonvolatile components of the resin composition are taken as 100% by mass.

[12] The resin composition according to any one of [1] to

[11] , wherein the content of component (C) is 50 to 90% by mass when the nonvolatile components of the resin composition are taken as 100% by mass.

[13] A cured product of any of the resin compositions described in [1] to

[12] .

[14] A semiconductor chip package comprising a cured product of any of the resin compositions described in [1] to

[12] .

[15] A fan-out type semiconductor chip package as described in

[14] .

[16] A semiconductor device comprising a cured product of any of the resin compositions described in [1] to

[12] .

[17] A step of forming a resin composition layer containing the resin composition described in any of [1] to

[12] on a semiconductor chip by compression molding, and A step of thermally curing the resin composition layer, A method for manufacturing semiconductor chip packages, including [the specified component]. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a resin composition that can simultaneously achieve suppression of warping, improvement of filling ability into gaps and gaps between electrodes, and improvement of adhesion, as well as a cured product obtained using the resin composition, a printed circuit board, a semiconductor chip package, a semiconductor device, a method for manufacturing a printed circuit board, and a method for manufacturing a semiconductor chip package. [Modes for carrying out the invention]

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples listed below, and may be implemented with modifications as appropriate without departing from the scope of the claims and their equivalents.

[0011] In the following explanation, the notations "XX or greater and YY or less" or "XX~YY" that represent numerical ranges mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way.

[0012] In the following explanation, "non-volatile components" refers to the components of the resin composition other than the organic solvents described later. Furthermore, "resin components" refers to the non-volatile components of the resin composition other than the inorganic fillers described later.

[0013] In the following descriptions, the phrase "may have substituents" when referring to a compound or group means, unless otherwise specified, both cases where the hydrogen atoms of the compound or group are not substituted by substituents, and cases where some or all of the hydrogen atoms of the compound or group are substituted by substituents. Furthermore, when describing the number of constituent atoms or carbon atoms of the compound or group, unless otherwise specified, the number of constituent atoms or carbon atoms of substituents is not included.

[0014] [Resin composition] The resin composition of the present invention contains (A1) an epoxy resin represented by a specific structure, (A2) a liquid epoxy resin having an aromatic skeleton, (B) a curing accelerator, and (C) an inorganic filler, wherein the mass ratio of component (A1) to component (A2) [(A1) component / (A2) component] is 0.1 to 3.5. By incorporating components (A1), (A2), (B), and (C) into the resin composition and setting the mass ratio of component (A1) to component (A2) within a specific range, a resin composition can be obtained that simultaneously achieves suppression of warping, improvement of filling ability into gaps and gaps between electrodes, and improvement of adhesion. The inventors have also confirmed that the resin composition of the present invention has excellent workability during compression molding, can suppress flow marks during molding, and has excellent storage stability. The resin composition may also contain any additional components in combination with components (A1), (A2), (B), and (C). Examples of optional components include epoxy resins that do not fall under either component (A1) or component (A2) (hereinafter referred to as "component (A3)"), (D) polymers that meet specific conditions, (E) silane coupling agents, (F) curing agents, (G) organic solvents, (H) other additives, etc.

[0015] The following provides a detailed explanation of each component included in the resin composition.

[0016] <(A1) Epoxy resin represented by a specific structure> The resin composition of the present invention contains (A1) an epoxy resin represented by the following formula (a-3). Component (A1) is an epoxy resin having a polyalkylene oxy structure and a bisphenol structure. By containing component (A1) in the resin composition, warping of the cured product of the resin composition can be suppressed. An epoxy resin is a curable resin having epoxy groups. [ka] (In the formula, Each Ar ring independently represents an aromatic carbon ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms. X represents an alkylene group with 1 to 20 carbon atoms. Each Y independently represents an alkylene group with 1 to 10 carbon atoms. m1 and m2 each independently represent integers between 0 and 20, and at least one of m1 and m2 is 1 or greater. * represents a bond.

[0017] In the present invention, "bisphenol" means "a compound having two hydroxyaryl groups in its molecule," and "bisphenol structure" refers to "the structure of bisphenol with the hydrogen atoms of the two hydroxyl groups removed." Examples of bisphenols in the bisphenol structure include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C2, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, bisnaphthol, biphenol, bixylenol, binaphthol, etc., with bisphenol A, bisphenol F, bisphenol AF, or biphenol being preferred, and bisphenol A being more preferred.

[0018] In formula (a-3), each Ar ring independently represents an aromatic carbocyclic ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms. An "aromatic ring" means a ring that follows Hückel's rule, in which the number of electrons in the π-electron system on the ring is 4r+2 (where r is a natural number), and includes monocyclic aromatic rings and fused aromatic rings formed by the fusion of two or more monocyclic aromatic rings. Monocyclic aromatic rings are preferred as aromatic rings. An aromatic carbocyclic ring means an aromatic ring having only carbon atoms as ring constituent atoms. Benzene rings or naphthalene rings are preferred as aromatic carbocyclic rings, with benzene rings being more preferred. When the Ar ring is a benzene ring, the relationship between the substitution position of X and the oxygen atom in formula (a-3) may be ortho, meta, or para, with the para position being preferred.

[0019] The aromatic carbocyclic rings in ring Ar may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms. That is, each ring Ar is independently an aromatic carbocyclic ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms, and it is preferable that each ring Ar is an aromatic carbocyclic ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms.

[0020] The alkyl group is a linear (linear or branched) alkyl group or a cyclic alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 1. Examples of linear alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, hexyl group, 2-ethylhexyl group, octyl group, and decyl group, with methyl group, ethyl group, n-propyl group, or isopropyl group being preferred, methyl group or ethyl group being more preferred, and methyl group being even more preferred. Examples of cyclic alkyl groups include cyclopentyl group, cyclohexyl group, and cyclooctyl group.

[0021] An aryl group is a group obtained by removing one hydrogen atom from the aromatic ring of an aromatic compound. The number of carbon atoms in an aryl group is preferably 1 to 10, more preferably 3 to 10, even more preferably 5 to 10, and particularly preferably 6 to 10. Examples of aryl groups include phenyl, naphthyl, thienyl, pyrrolyl, furanyl, furyl, pyridyl, pyridadinyl, pyrimidyl, pyrazinyl, triazinyl, pyrrolidyl, piperidyl, quinolyl, and isoquinolyl groups, with phenyl or naphthyl being preferred, and phenyl being more preferred.

[0022] In one embodiment, it is preferable that the aromatic carbon ring in the Ar ring does not have substituents that do not correspond to either X or the oxygen atom as expressed in formula (a-3). Hereinafter, an aromatic carbon ring that does not have substituents that do not correspond to either X or the oxygen atom as expressed in formula (a-3) will simply be referred to as an "aromatic carbon ring". That is, it is preferable that the Ar ring is an aromatic carbon ring having 6 to 10 carbon atoms.

[0023] In formula (a-3), X represents an alkylene group having 1 to 20 carbon atoms. The number of carbon atoms in the alkylene group in X is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and particularly preferably 3. Examples of alkylene groups in X include a methylene group, an ethylene group, an ethylidene group, a 1,2-propylene group, a 1,3-propylene group, a 1,1-propyridene group, a 2,2-propyridene group, etc., with a methylene group or a 2,2-propyridene group being preferred, and a 2,2-propyridene group being more preferred.

[0024] In the present invention, "alkylene oxy" means a divalent group in which an oxygen atom is bonded to one or both of the bonds of an alkylene group, and "polyalkylene oxy structure" means a structure having one or more repeating alkylene oxy units. Examples of polyalkylene oxy structures include polyethylene oxy structures, polypropylene oxy structures, and polybutylene oxy structures, with polyethylene oxy structures or polypropylene oxy structures being more preferred, and polypropylene oxy structures being even more preferred.

[0025] In formula (a-3), Y independently represents an alkylene group having 1 to 10 carbon atoms. The lower limit of the number of carbon atoms in the alkylene group in Y is preferably 2 or more. The upper limit of the number of carbon atoms in the alkylene group in Y is preferably 5 or less, more preferably 4 or less, and still preferably 3 or less. Examples of alkylene groups in Y include ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, and 1,4-butylene groups, with ethylene, 1,2-propylene, or 1,4-butylene groups being more preferred, ethylene or 1,2-propylene groups being even more preferred, and 1,2-propylene groups being particularly preferred.

[0026] In formula (a-3), m1 and m2 each independently represent integers between 0 and 20. m1 and m2 are preferably between 0 and 10, more preferably between 0 and 5, and even more preferably between 0 and 3. Also, at least one of m1 and m2 is 1 or greater. It is preferable that both m1 and m2 are 1 or greater. The sum of m1 and m2 (m1+m2) is between 1 and 40, preferably between 1 and 20, more preferably between 1 and 10, and even more preferably between 1 and 5.

[0027] Among these, the epoxy resin in which component (A1) is an aromatic carbon ring having 6 to 10 carbon atoms, in formula (a-3), X is an alkylene group having 1 to 5 carbon atoms, Y is an alkylene group having 2 to 4 carbon atoms independently, and the ring Ar may each independently have substituents selected from alkyl groups having 1 to 10 carbon atoms, is more preferred, and the epoxy resin represented by (a-3-1) below is more preferred. [ka] (In the formula, m1 and m2 each independently represent integers between 0 and 20, and at least one of m1 and m2 is 1 or greater.)

[0028] (A1) A commercially available product can be used as component (A1). Examples of commercially available products include "EP-4000L", "EP-4000S", "EP-4003S", "EP-4010S", and "EP-4010L" from ADEKA Corporation. Component (A1) can also be produced by reacting the corresponding bisphenol, alkylene oxide, and epichlorohydrin. The above "alkylene oxide" refers to an epoxy compound in which two bonds of an alkylene group are linked via an oxygen atom.

[0029] <(A2) Liquid epoxy resin having an aromatic skeleton> The resin composition of the present invention contains (A2) a liquid epoxy resin having an aromatic skeleton. However, components corresponding to component (A1) are excluded from component (A2). In the present invention, "liquid epoxy resin" means "an epoxy resin that is liquid at a temperature of 20°C".

[0030] Examples of component (A2) include bixylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, cresol novolac-type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, tetraphenylethane-type epoxy resin, phenolphthalein-type epoxy resin, fluorene structure-containing epoxy resin, etc., with bisphenol A-type epoxy resin or naphthalene-type epoxy resin being preferred. Component (A2) may be used alone or in combination of two or more types.

[0031] Component (A2) preferably contains an epoxy resin having two or more epoxy groups in one molecule. The proportion of the epoxy resin having two or more epoxy groups in one molecule, relative to 100% by mass of component (A2), is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0032] (A2)Specific examples of components include "EX-992L" from Nagase ChemteX, "YX7400" from Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" from DIC Corporation (naphthalene-type epoxy resin); "828US", "jER828EL", "828EL", "825", and "Epicoat 828EL" from Mitsubishi Chemical Corporation, "850", and "EXA-850CRP" from DIC Corporation (bisphenol A-type epoxy resin); "jER807" and "1750" from Mitsubishi Chemical Corporation (bisphenol F-type epoxy resin); and "jER152" from Mitsubishi Chemical Corporation (phenol novolac-type epoxy resin). Examples of epoxy resins include: Mitsubishi Chemical's "630," "630LSD," and "604" (glycidylamine type epoxy resins with aromatic skeletons); ADEKA's "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resins with aromatic skeletons); Nippon Steel Chemical & Material's "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin with aromatic skeletons); and Osaka Gas Chemical's "EG-280" (fluorene structure-containing epoxy resin).

[0033] <Epoxy resin that does not fall under either component (A1) or component (A2)> The resin composition of the present invention may contain, as an optional component, an epoxy resin that does not fall under either component (A1) or component (A2) (hereinafter referred to as "component (A3)").

[0034] (A3) Examples of components include bixylenol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, bisphenol AF-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol novolac-type epoxy resin, phenol novolac-type epoxy resin, tert-butyl-catechol-type epoxy resin, naphthalene-type epoxy resin, naphthol-type epoxy resin, anthracene-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, and phenol aral. Examples include kill-type epoxy resins, biphenyl-type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, isocyanurate-type epoxy resins, phenolphthaleimidine-type epoxy resins, glycyrrhizol-type epoxy resins, alkylene oxy skeleton-containing epoxy resins, fluorene-structure-containing epoxy resins, etc., with dicyclopentadiene-type epoxy resins being preferred. Component (A3) may be used alone or in combination of two or more types.

[0035] The resin composition of the present invention preferably contains an epoxy resin having two or more epoxy groups in one molecule as component (A3). The proportion of the epoxy resin having two or more epoxy groups in one molecule per 100% by mass of component (A3) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0036] Epoxy resins include epoxy resins that are liquid at 20°C (liquid epoxy resins) and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition of the present invention may contain only liquid epoxy resin as component (A3), or only solid epoxy resin, or both liquid epoxy resin and solid epoxy resin. In one embodiment, it is preferable that component (A3) contains liquid epoxy resin.

[0037] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0038] Examples of liquid epoxy resins in component (A3) include glycyrol-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cyclic aliphatic glycidyl ethers, epoxy resins having a butadiene structure, dicyclopentadiene-type epoxy resins, and alkylene oxy-backbone-containing epoxy resins, with dicyclopentadiene-type epoxy resins being preferred.

[0039] Specific examples of liquid epoxy resins in component (A3) include "ED-523T" (glycyrol-type epoxy resin) from ADEKA Corporation; "EP-4088S" (dicyclopentadiene-type epoxy resin) from ADEKA Corporation; "EX-991L" (alkylene oxy skeleton-containing epoxy resin) from Nagase ChemteX Corporation; "Celoxide 2021P" (alicyclic epoxy resin with an ester skeleton) from Daicel Corporation; "PB-3600" from Daicel Corporation; "JP-100" and "JP-200" (epoxy resins with a butadiene structure) from Nippon Soda Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) from Nippon Steel Chemical & Material Co., Ltd.; and "EX-201" (cyclic aliphatic glycidyl ether) from Nagase ChemteX Corporation.

[0040] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups per molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups per molecule is more preferred.

[0041] Examples of solid epoxy resins in component (A3) include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, naphthol novolac-type epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, phenol aralkyl-type epoxy resin, tetraphenylethane-type epoxy resin, phenolphthalein-type epoxy resin, and fluorene-structure-containing epoxy resins.

[0042] Specific examples of solid epoxy resins in component (A3) include DIC's "HP4032H" (naphthalene-type epoxy resin); DIC's "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resins); DIC's "N-690" and "N-695" (cresol novolac-type epoxy resins); DIC's "HP-7200", "HP-7200HH", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resins); DIC's "EXA-7311" and "EXA-73 11-G3", EXA-7311-G4", EXA-7311-G4S", HP6000 (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd.'s "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC7000L" (naphthol novolac type epoxy resin); Nippon Kayaku Co., Ltd.'s "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin); Nippon Steel Chemical & Material Co., Ltd.'s "ESN475V", "ESN4100V" Naphthalene-type epoxy resin; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" manufactured by Mitsubishi Chemical Corporation Examples include (phenol aralkyl type epoxy resin); "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene structure-containing epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; and "WHR991S" (phenolphthaleinidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These can be used individually or in combination of two or more types.

[0043] The epoxy equivalents of components (A1), (A2), and (A3) are preferably 50 to 5,000 g / eq., more preferably 50 to 3,000 g / eq., even more preferably 80 to 2,000 g / eq., and particularly preferably 110 to 1,000 g / eq. By setting the epoxy equivalents within the above range, the crosslinking density of the cured product can be sufficiently increased. The epoxy equivalent is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0044] The weight-average molecular weight (Mw) of components (A1), (A2), and (A3) is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight of the epoxy resin can be measured as a polystyrene equivalent by gel permeation chromatography (GPC).

[0045] The total content of component (A1) and component (A2) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 97% by mass or more, when the total content of component (A1), component (A2), and component (B) is set to 100% by mass. The upper limit is preferably 99.9% by mass or less, and more preferably 99% by mass or less.

[0046] The total content of component (A1) and component (A2) is preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, when the resin component of the resin composition is considered to be 100% by mass, from the viewpoint of obtaining the effects of the present invention. The upper limit is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0047] The total content of components (A1) and (A2) is preferably 5% by mass or more, more preferably 10% by mass or more, 12% by mass or more, or 14% by mass or more, and even more preferably 15% by mass or more, when the nonvolatile components of the resin composition are considered to be 100% by mass, from the viewpoint of obtaining the effects of the present invention. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, or 25% by mass or less, and particularly preferably 20% by mass or less.

[0048] Regarding the content of component (A1), from the viewpoint of significantly obtaining the effects of the present invention, when the total content of components (A1), (A2), and (B) is set to 100% by mass, it is preferably 5% by mass or more or 10% by mass or more, more preferably 15% by mass or more or 20% by mass or more, even more preferably 25% by mass or more or 30% by mass or more, and particularly preferably 35% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less.

[0049] (A1) As for the content of component (A1), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component of the resin composition is considered to be 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more or 25% by mass or more, and particularly preferably 30% by mass or more or 35% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 45% by mass or less or 40% by mass or less.

[0050] (A1) As for the content of component (A1), from the viewpoint of significantly obtaining the effects of the present invention, when the nonvolatile components of the resin composition are considered to be 100% by mass, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, and particularly preferably 6% by mass or more or 7% by mass or more. The upper limit is preferably 50% by mass or less or 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less or 9% by mass or less.

[0051] Regarding the content of component (A2), from the viewpoint of significantly obtaining the effects of the present invention, when the total content of components (A1), (A2), and (B) is taken as 100% by mass, it is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 95% by mass or less or 90% by mass or less, more preferably 80% by mass or less or 70% by mass or less, even more preferably 65% ​​by mass or less, and particularly preferably 60% by mass or less.

[0052] (A2) Regarding the content of component (A2), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component of the resin composition is considered to be 100% by mass, it is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and particularly preferably 50% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 65% ​​by mass or less or 60% by mass or less.

[0053] (A2) Regarding the content of component (A2), from the viewpoint of significantly obtaining the effects of the present invention, when the nonvolatile components of the resin composition are considered to be 100% by mass, the content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and particularly preferably 7% by mass or 9% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 12% by mass or less.

[0054] The mass ratio of component (A1) to component (A2) [(A1) component / (A2) component] is 0.1 to 3.5. The lower limit of the mass ratio [(A1) component / (A2) component] is preferably 0.12 or higher, more preferably 0.15 or higher, even more preferably 0.18 or higher, particularly preferably 0.2 or higher, 0.3 or higher, 0.4 or higher, 0.5 or higher, or 0.6 or higher, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 3.2 or lower or 3 or lower, more preferably 2.8 or lower or 2.5 or lower, even more preferably 2.2 or lower or 2 or lower, particularly preferably 1.8 or lower or 1.5 or lower.

[0055] When the resin composition of the present invention contains component (A3), the content of component (A3) is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass, and particularly preferably 6% by mass or less, when the nonvolatile components of the resin composition are taken as 100% by mass, from the viewpoint of obtaining the effects of the present invention to be significantly apparent. The lower limit is not particularly limited and can be 0.1% by mass or more, 1% by mass or more, etc.

[0056] When the resin composition of the present invention contains component (A3), the total content of components (A1), (A2), and (A3) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, when the nonvolatile components of the resin composition are taken as 100% by mass, from the viewpoint of obtaining the effects of the present invention to be significantly apparent. The upper limit is preferably 90% by mass or less or 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less or 25% by mass or less, and particularly preferably 20% by mass or less.

[0057] <(B) Curing accelerator> The resin composition of the present invention contains (B) a curing accelerator. The curing accelerator (B) functions as a curing catalyst that accelerates the curing of components (A1), (A2), and (A3).

[0058] (B) Examples of curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. (B) The curing accelerator preferably contains an imidazole-based curing accelerator. (B) The curing accelerator may be used alone or in combination of two or more types.

[0059] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine; pyridines such as 4-dimethylaminopyridine; benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol; 1,8-diazabicyclo(5,4,0)-undecene; and others. Pyridines are preferred, and 4-dimethylaminopyridine is more preferred. These may be used individually or in combination of two or more.

[0060] As amine-based curing accelerators, commercially available products may be used, such as "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd. and "DMAP" manufactured by Koei Chemical Industry Co., Ltd.

[0061] Examples of phosphorus-based curing accelerators include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromelitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, and tetraphenylphosphonium bromide. Aromatic phosphonium salts such as tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition products such as triphenylphosphine-p-benzoquinone addition products; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris(4-ethylphenyl)phosphine, tris(4-propylphenyl)phosphine, tris(4-isopropylphenyl)phosphine, tris(4-butylphenyl)phosphine, tris(4-tert-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples include aromatic phosphines such as tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether. These may be used individually or in combination of two or more.

[0062] Examples of urea-based curing accelerators include aliphatic dimethylureas such as 1,1-dimethylurea, 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas such as toluenebisdimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] are examples. These may be used individually or in combination of two or more.

[0063] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. These may be used individually or in combination of two or more types.

[0064] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazol-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Midazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride Examples include imidazole compounds such as lide, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins. 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, or 2-ethyl-4-methylimidazole are preferred, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole or 1-(2-cyanoethyl)-2-undecylimidazole are more preferred.

[0065] Examples of commercially available imidazole-based curing accelerators include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2P4MZ", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" from Shikoku Chemicals Corporation; and "P200-H50" from Mitsubishi Chemical Corporation. These may be used individually or in combination of two or more types.

[0066] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used individually or in combination of two or more.

[0067] In one embodiment, the resin composition of the present invention preferably contains a curing accelerator having a cyano group as component (B). Since the cyano group is an electron-withdrawing substituent, the presence of a cyano group in the curing accelerator makes it less nucleophilic, allowing the activity of the curing accelerator to be adjusted to an appropriate range. As a result, it is possible to prevent the curing reaction from progressing during storage of the resin composition and causing it to thicken, thereby improving the storage stability of the resin composition. Furthermore, by including a curing accelerator having a cyano group in the resin composition, the formation of flow marks when the resin composition is cured can be suppressed more effectively. Examples of curing accelerators having a cyano group include imidazole-based curing accelerators having a cyano group, phosphorus-based curing accelerators having a cyano group, amine-based curing accelerators having a cyano group, guanidine-based curing accelerators having a cyano group, metal-based curing accelerators having a cyano group, and peroxide-based curing accelerators having a cyano group, with imidazole-based curing accelerators having a cyano group being preferred. A curing accelerator containing a cyano group may be used alone or in combination of two or more types.

[0068] In one embodiment of the present invention, the curing accelerator having a cyano group is preferably a curing accelerator represented by the following formula (b-1). [ka] (In the formula, R 1 , R 2 and R 3 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms. Z represents an alkylene group with 1 to 20 carbon atoms, or an arylene group with 1 to 20 carbon atoms.

[0069] In formula (b-1), R 1 , R 2 and R 3 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 1 to 20 carbon atoms.

[0070] The alkyl group is a linear (straight-chain or branched) alkyl group or a cyclic alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 12. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, an undecyl group, etc. Among them, a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an undecyl group is preferable, a methyl group, an ethyl group or an undecyl group is more preferable, and a methyl group or an ethyl group is even more preferable. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc.

[0071] The aryl group is a group obtained by removing one hydrogen atom from an aromatic ring of an aromatic compound. The number of carbon atoms in the aryl group is preferably 1 to 10, more preferably 3 to 10, even more preferably 5 to 10, and particularly preferably 6 to 10. Examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, a pyrrolyl group, a furanyl group, a furyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, a pyrrolidyl group, a piperidyl group, a quinolyl group, an isoquinolyl group, etc. Among them, a phenyl group or a naphthyl group is preferable, and a phenyl group is even more preferable.

[0072] Among these, R 1 、R 2 and R 3 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, an undecyl group or a phenyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group or an undecyl group.

[0073] In formula (b-1), Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms. Z is preferably an alkylene group having 1 to 20 carbon atoms.

[0074] The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2. Examples of alkylene groups include methylene, ethylene, ethylidene, 1,2-propylene, 1,3-propylene, 1,1-propylene, 2,2-propylene, 1,2-butylene, 1,3-butylene, and 1,4-butylene groups, with ethylene, 1,3-propylene, or 1,4-butylene groups being more preferred, and ethylene being even more preferred.

[0075] An arylene group is an aromatic compound from which two hydrogen atoms have been removed from the aromatic ring. The number of carbon atoms in an arylene group is preferably 1 to 10, more preferably 3 to 10, even more preferably 5 to 10, and particularly preferably 6 to 10. Examples of arylene groups include phenylene, naphthylene, thienylene, pyrrolylene, furanylene, flurene, pyridylene, pyridadinylene, pyrimidiylene, pyrazinylene, triazinylene, pyrrolidylene, piperidylene, quinolylene, isoquinolylene, etc., with phenylene or naphthylene being preferred, and phenylene being more preferred.

[0076] Examples of curing accelerators having a cyano group include 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-undecylimidazolium trimellitate, and 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, with 1-(2-cyanoethyl)-2-methylimidazole, 1-(2-cyanoethyl)-2-undecylimidazole, or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole being preferred, and 1-(2-cyanoethyl)-2-undecylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole being more preferred.

[0077] Commercially available curing accelerators containing cyano groups can be used, such as "2E4MZ-CN", "C11Z-CN", "2MZ-CN", "2PZ-CN", and "2PZCNS-PW" manufactured by Shikoku Chemicals, Inc.

[0078] Regarding the content of component (B), from the viewpoint of significantly obtaining the effects of the present invention, when the total content of components (A1), (A2), and (B) is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3.5% by mass or less or 3% by mass or less.

[0079] (B) As for the content of component (B), from the viewpoint of significantly obtaining the effects of the present invention, when the resin component of the resin composition is considered to be 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more or 0.5% by mass or more, even more preferably 0.6% by mass or more, 0.8% by mass or 1% by mass or more, and particularly preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3.5% by mass or less or 3% by mass or less.

[0080] (B) Regarding the content of component (B), from the viewpoint of significantly obtaining the effects of the present invention, when the nonvolatile components of the resin composition are taken as 100% by mass, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more or 0.3% by mass or more, and particularly preferably 0.4% by mass or more. The upper limit is 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less or 0.6% by mass or less.

[0081] The lower limit of the mass ratio of component (B) to component (A1) [(B) component / (A1) component] is preferably 0.001 or higher, more preferably 0.01 or higher, even more preferably 0.03 or higher, and particularly preferably 0.05 or higher, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 1 or lower, more preferably 0.5 or lower or 0.2 or lower, even more preferably 0.1 or lower, and particularly preferably 0.07 or lower.

[0082] From the viewpoint of significantly obtaining the effects of the present invention, the total content of components (A1), (A2), and (B) is preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, when the resin component of the resin composition is considered to be 100% by mass. The upper limit may be 100% by mass or less, 99% by mass or less, 98% by mass or less, 97% by mass or less, etc.

[0083] From the viewpoint of significantly obtaining the effects of the present invention, the total content of components (A1), (A2), and (B) is preferably 5% by mass or more, more preferably 10% by mass or more, 12% by mass or more, or 14% by mass or more, even more preferably 15% by mass or more, and particularly preferably 17% by mass or more, when the nonvolatile components of the resin composition are considered to be 100% by mass. The upper limit can be 90% by mass or less, 60% by mass or less, 40% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, etc.

[0084] <(C) Inorganic filler> The resin composition of the present invention contains (C) an inorganic filler. The (C) inorganic filler is usually included in the resin composition in granular form. The inclusion of component (C) in the resin composition can result in a cured product exhibiting good dielectric properties (low dielectric loss tangent) and further suppress warping of the cured product.

[0085] Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum silicate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Spherical silica is preferred. Inorganic fillers may be used individually or in combination of two or more types.

[0086] Examples of commercially available inorganic fillers include "SP60-05" and "SP507-05" from Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" from Admatex Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" from Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" from Tokuyama Corporation; and "Cellspheres" and "MGH-005" from Taiheiyo Cement Corporation.

[0087] (C) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, particularly preferably 0.2 μm or more, 0.3 μm or more, or 0.4 μm or more. (C) The maximum cut diameter of the inorganic filler is preferably 100 μm or less, more preferably 50 μm or less or 20 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less.

[0088] (C) The average particle size of inorganic fillers can be measured by the laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis using a laser diffraction-scattering particle size distribution analyzer, and the median diameter can be used as the average particle size. A sample can be prepared by weighing 100 mg of inorganic filler and 10 g of methyl ethyl ketone into a vial and dispersing them with ultrasound for 10 minutes. The light source wavelength used in the laser diffraction-type particle size distribution analyzer can be blue or red, and measurement can be performed using a flow cell method. An example of a laser diffraction-type particle size distribution analyzer is the "LA-960" manufactured by Horiba, Ltd.

[0089] The specific surface area of ​​the inorganic filler is not particularly limited, but is preferably 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, 3m 2 / g or more or 4m 2 The specific surface area is 1 / g or more. The upper limit of the specific surface area is not particularly limited, but is preferably 80m². 2 / g or less, more preferably 60m 2 / g or less, more preferably 50m 2 / g or less or 40m 2 / g or less, particularly preferably 30m 2 / g or less or 20m 2The value is less than / g. The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the sample surface using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec Co., Ltd.) according to the BET method, and then calculating the specific surface area using the BET multipoint method.

[0090] (C) The inorganic filler is preferably surface-treated with a surface treatment agent. Surface treatment can improve the moisture resistance and dispersibility of the (C) inorganic filler.Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl-based silane coupling agents such as p-styryltrimethoxysilane; and 3-methacrylate. Methacryl-based silane coupling agents such as roxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acrylic-based silane coupling agents such as 3-acryloxypropyltrimethoxysilane; N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Amino-based silane coupling agents such as propyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate-based silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; and ureido-based coupling agents such as 3-ureidopropyltrialkoxysilane. Examples of silane coupling agents include mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate-based silane coupling agents such as 3-isocyanatetopropyltriethoxysilane; acid anhydride-based silane coupling agents such as 3-trimethoxysilylpropylsuccinic anhydride; alkoxysilane compounds such as methyltrimethoxysilane and phenyltrimethoxysilane; silazane compounds such as hexamethyldisilazane; and the like.As the surface treatment agent, a silane coupling agent is preferred, an amino-based silane coupling agent is more preferred, and N-phenyl-3-aminopropyltrimethoxysilane is even more preferred. Furthermore, the surface treatment agent may be used alone, or two or more may be used in any ratio.

[0091] Examples of commercially available surface treatment agents include "KBM-403" (3-glycidoxypropyltrimethoxysilane), "KBM-803" (3-mercaptopropyltrimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), and "SZ-31" (hexamethyldisilazane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0092] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment by the surface treatment agent is preferably within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent.

[0093] The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of ​​the inorganic filler should be 0.02 mg / m². 2 The above is preferred, and 0.1 mg / m² 2 The above is more preferable, 0.2 mg / m² 2 The above is even more preferable. The upper limit is 1.0 mg / m². 2 The following is preferred: 0.8 mg / m² 2 The following is more preferable: 0.5 mg / m² 2The following is even more preferable. The amount of carbon per unit surface area of ​​the inorganic filler can be measured after washing the inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)) after surface treatment. Specifically, a sufficient amount of MEK as the solvent is added to the inorganic filler that has been surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant liquid and drying the solids, the amount of carbon per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0094] (C) The content of component (C) is preferably 50% by mass or more, more preferably 60% by mass or more or 65% by mass or more, and even more preferably 70% by mass or more, 75% by mass or more, 76% by mass or more, 78% by mass or more or 80% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass, from the viewpoint of reducing the dielectric loss tangent of the cured product and reducing the thermal expansion coefficient of the cured product. The upper limit is not particularly limited, but for example it may be 90% by mass or less, 85% by mass or less.

[0095] <(D) Polymers that meet specific conditions> The resin composition of the present invention may contain, as an optional component, a polymer that satisfies the following conditions (d1) to (d3) (hereinafter referred to as "component (D)"), and it is preferable that it contains component (D). By containing component (D) in the resin composition, warping of the cured product of the resin composition can be further suppressed and workability during compression molding can be improved. Condition (d1): The number-average molecular weight is between 1,000 and 150,000. Condition (d2): Liquid at 25°C, or glass transition temperature is 25°C or lower. Condition (d3): Has a polysiloxane structure.

[0096] <<Condition (d3)>> Component (D) has a polysiloxane structure. The polysiloxane structure is preferably a polydialkylsiloxane structure, and the alkyl group of the polydialkylsiloxane structure is preferably a methyl group.

[0097] <<Condition (d4)>> In one embodiment, from the viewpoint of further improving the ability to fill gaps and spaces between electrodes, further improving adhesion, improving workability during compression molding, and suppressing flow marks, it is preferable that component (D) is a polymer that further satisfies the following condition (d4). Condition (d4): Has a polyalkylene oxy structure.

[0098] The polysiloxane structure and the polyalkylene oxy structure may be included in the main chain or the side chain of component (D). That is, examples of component (D) that satisfy condition (d4) include polymers obtained by copolymerizing the polysiloxane structure and the polyalkylene oxy structure, and polymers in which a portion of the side chain of the silicone is substituted with a polyether. By substituting a portion of the side chain of the silicone of component (D) with a polyether, the compatibility between component (D) and other components can be improved. In one embodiment, as component (D) that satisfies condition (d4), it is preferable that a polymer in which a portion of the alkyl group of the polydialkylsiloxane is substituted with a polyether. It is preferable that the alkyl group of the polydialkylsiloxane is a methyl group. Examples of polyethers to be substituted include polyethylene glycol and polypropylene glycol, with polyethylene glycol being preferred.

[0099] <<Condition(d1)>> Component (D) has a number-average molecular weight (Mn) of 1,000 to 150,000. By satisfying condition (d1), warping of the cured product can be further suppressed. The number-average molecular weight (Mn) of component (D) is preferably 1,200 or more, more preferably 1,500 or more, even more preferably 2,000 or more, 2,500 or more, 3,000 or more, 3,500 or more, or 4,000 or more. The upper limit of the number-average molecular weight (Mn) is preferably 120,000 or less or 100,000 or less, more preferably 80,000 or less or 50,000 or less, even more preferably 20,000 or less, 10,000 or less, or 8,000 or less, and particularly preferably 7,000 or less, 6,000 or less, or 5,000 or less. The number-average molecular weight (Mn) can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0100] The weight-average molecular weight (Mw) of component (D) is preferably 1,000 or more, or 1,200 or more, more preferably 1,500 or more, even more preferably 2,000 or more, 2,500 or more, 3,000 or more, 3,500 or more, or 4,000 or more. The upper limit of the weight-average molecular weight (Mw) is preferably 150,000 or less, 120,000 or less, or 100,000 or less, more preferably 80,000 or less, or 50,000 or less, even more preferably 20,000 or less. The weight-average molecular weight (Mw) can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0101] <<Condition(d2)>> Component (D) is liquid at 25°C, or has a glass transition temperature of 25°C or lower. By satisfying condition (d2), warping of the cured product can be further suppressed. Here, for polymers in which multiple glass transition temperatures are observed, if the lowest glass transition temperature is 25°C or lower, it falls under the category of "glass transition temperature of 25°C or lower".

[0102] If the glass transition temperature of component (D) is 25°C or lower, the glass transition temperature is preferably 20°C or lower, more preferably 15°C or lower. The lower limit of the glass transition temperature is not particularly limited, but it can usually be -50°C or higher. Also, if component (D) is liquid at 25°C, it is preferably liquid at 20°C, more preferably at 15°C. The glass transition temperature can be measured by DSC (Differential Scanning Calorimetry).

[0103] Component (D) preferably has functional groups that can react with epoxy resins, etc., in order to achieve a cured product with high cohesive strength (intralayer adhesion strength) by reacting with epoxy resins, etc. Functional groups that can react with epoxy resins, etc., also include functional groups that appear upon heating.

[0104] In one preferred embodiment, the functional group that can react with epoxy resin, etc., is one or more functional groups selected from the group consisting of hydroxyl groups, carboxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups. Among these, one or more functional groups selected from the group consisting of hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, epoxy groups, isocyanate groups, and urethane groups are preferred, one or more functional groups selected from the group consisting of hydroxyl groups, acid anhydride groups, phenolic hydroxyl groups, and epoxy groups are more preferred, and a hydroxyl group is even more preferred.

[0105] (D)Specific examples of components include, for example, Shin-Etsu Chemical Co., Ltd.'s "KF-1002", "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017", "KF-6017P", "KF-6043", "KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF Examples include "-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", "KF-6025" (polymers having polysiloxane and polyalkylene oxy structures), and "X-22-162C" manufactured by Shin-Etsu Chemical Co., Ltd. (a silicone compound with a polydimethylsiloxane skeleton as the main chain and no polyalkylene oxy structure).

[0106] Of the commercially available products listed above, Shin-Etsu Chemical Co., Ltd.'s "KF-1002", "KF-6011", "KF-6011P", "KF-6012", "KF-6013", "KF-6015", "KF-6016", "KF-6017", "KF-6017P", "KF-6043", "KF-6004", "KF351A", "KF352A", "KF353", "KF354L", "KF355A", "KF615A", "KF945", "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X22-4515", "KF-6028", "KF-6028P", "KF-6038", "KF-6048", and "KF-6025" also fall under component (D) which satisfies condition (d4).

[0107] If the resin composition of the present invention contains component (D), the content of component (D) is preferably 0.1% by mass or more, 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, 2% by mass or more, and particularly preferably 2.2% by mass or more, when the total amount of resin components in the resin composition is 100% by mass, from the viewpoint of further suppressing warping of the cured product. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, 20% by mass or less, or 15% by mass or less, even more preferably 10% by mass or less, or 5% by mass or less, and particularly preferably 3% by mass or less, from the viewpoint of further improving adhesion.

[0108] If the resin composition of the present invention contains component (D), the content of component (D) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more, when the nonvolatile components in the resin composition are taken as 100% by mass, from the viewpoint of further suppressing warping of the cured product. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.8% by mass or less, from the viewpoint of further improving adhesion.

[0109] When the resin composition of the present invention contains component (D), the lower limit of the mass ratio of component (D) to component (A1) [(D) component / (A1) component] is preferably 0.001 or more, more preferably 0.01 or more, even more preferably 0.03 or more, and particularly preferably 0.05 or more, from the viewpoint of further suppressing warping of the cured product. The upper limit is preferably 2 or less, more preferably 1 or less or 0.5 or less, even more preferably 0.2 or less or 0.1 or less, and particularly preferably 0.08 or less, from the viewpoint of further improving adhesion.

[0110] When the resin composition of the present invention contains component (D), the lower limit of the mass ratio of component (D) to component (B) [(D) component / (B) component] is preferably 0.01 or more or 0.05 or more, more preferably 0.1 or more or 0.2 or more, even more preferably 0.3 or more or 0.5 or more, and particularly preferably 0.7 or more, 0.8 or more or 0.9 or more. The upper limit is preferably 100 or less or 50 or less, more preferably 30 or less or 20 or less, even more preferably 15 or less or 10 or less, and particularly preferably 8 or less, 6 or less or 5 or less.

[0111] <(E) Silane coupling agent> The resin composition of the present invention may contain (E) a silane coupling agent as an optional component, and it is preferable that it contains (E) a silane coupling agent. By containing (E) a silane coupling agent in the resin composition, the adhesion between the cured resin composition and the conductive layer, and the adhesion between the cured resin composition and the semiconductor chip can be further improved.

[0112] Examples of silane coupling agents include amino-based silane coupling agents, epoxy-based silane coupling agents, mercapto-based silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate-based coupling agents. Among these, epoxy-based silane coupling agents containing epoxy groups or mercapto-based silane coupling agents containing mercapto groups are preferred. By incorporating an epoxy-based silane coupling agent into the resin composition, the adhesion between the cured resin composition and the semiconductor chip can be further improved. By incorporating a mercapto-based silane coupling agent into the resin composition, the adhesion between the cured resin composition and the conductive layer can be further improved. Furthermore, one type of silane coupling agent may be used alone, or two or more types may be used in combination.

[0113] For example, commercially available silane coupling agents may be used. Examples of commercially available silane coupling agents include "KBM-403" (3-glycidoxypropyltrimethoxysilane), "KBM-803" (3-mercaptopropyltrimethoxysilane), "KBE-903" (3-aminopropyltriethoxysilane), "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), "KBM-4803" (long-chain epoxy type silane coupling agent), and "KBM-503" (3-methacryloxypropyltrimethoxysilane), all manufactured by Shin-Etsu Chemical Co., Ltd.

[0114] When the resin composition of the present invention contains (E) a silane coupling agent, the content of component (E) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 0.8% by mass or more, when the total amount of resin components in the resin composition is 100% by mass, from the viewpoint of obtaining the effects of the present invention to be significantly apparent. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less.

[0115] When the resin composition of the present invention contains (E) a silane coupling agent, the content of component (E) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.15% by mass or more, when the nonvolatile components in the resin composition are considered to be 100% by mass, from the viewpoint of obtaining the effects of the present invention to be significantly apparent. The upper limit is preferably 5% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

[0116] When the resin composition of the present invention contains (E) a silane coupling agent, the lower limit of the mass ratio of component (E) to component (A1) [(E) component / (A1) component] is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and particularly preferably 0.02 or more, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 1 or less, more preferably 0.5 or less, even more preferably 0.1 or less, and particularly preferably 0.05 or less.

[0117] When the resin composition of the present invention contains (E) a silane coupling agent, the lower limit of the mass ratio of component (E) to component (B) [(E) component / (B) component] is preferably 0.1 or higher, more preferably 0.2 or higher, even more preferably 0.5 or higher, and particularly preferably 0.8 or higher, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit is preferably 10 or lower, more preferably 8 or lower, even more preferably 5 or lower, and particularly preferably 3 or lower or 2 or lower.

[0118] When the resin composition of the present invention contains component (D) and silane coupling agent (E), the lower limit of the mass ratio of component (E) to component (D) [(E) / (D)] is preferably 0.01 or higher, more preferably 0.05 or higher, even more preferably 0.1 or higher, and particularly preferably 0.2 or higher or 0.3 or higher, from the viewpoint of obtaining the effects of the present invention to a remarkable degree. The upper limit is preferably 5 or lower, more preferably 2 or lower, even more preferably 1 or lower, and particularly preferably 0.8 or lower or 0.5 or lower.

[0119] <(F) Hardener> The resin composition of the present invention may contain (F) a curing agent as an optional component. The curing agent is not particularly limited as long as it has the function of curing epoxy resin, and examples include acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. The curing agent may be used alone or in combination of two or more types.

[0120] In particular, from the viewpoint of realizing a resin composition that exhibits good fluidity during filling and sealing, it is preferable that the curing agent includes one or more curing agents (f1) selected from the group consisting of acid anhydride-based curing agents and amine-based curing agents.

[0121] Suitable curing agents (f1) include acid anhydride-based curing agents having one or more acid anhydride groups in one molecule.

[0122] Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexen-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, and bensofenone tetracarboxylic acid di Examples include anhydrides, biphenyltetracarboxylic acid dianhydride, naphthalenetetracarboxylic acid dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid.

[0123] Examples of commercially available acid anhydride-based curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0124] Suitable curing agents (f1) include amine-based curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, and the like.

[0125] Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxy Examples include bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc.

[0126] Examples of commercially available amine-based curing agents include "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" from Nippon Kayaku Co., Ltd., and "Epicure W" from Mitsubishi Chemical Corporation.

[0127] As a curing agent, one or more curing agents (f2) selected from the group consisting of phenolic curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents may also be mentioned.

[0128] From the viewpoint of heat resistance and water resistance, phenolic and naphthol curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion to the conductive layer, nitrogen-containing phenolic and nitrogen-containing naphthol curing agents are preferred, and triazine skeleton-containing phenolic and triazine skeleton-containing naphthol curing agents are more preferred. Specific examples of phenolic and naphthol curing agents include, for example, "MEH-7700", "MEH-7810", "MEH-7851", and "MEH-8000H" from Meiwa Kasei Co., Ltd.; "NHN", "CBN", and "GPH" from Nippon Kayaku Co., Ltd.; and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-495V", and "SN-37" from Nippon Steel Chemical & Material Co., Ltd. Examples include "5", "SN-395", "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", "KA-1165" from DIC Corporation, and "GDP-6115L", "GDP-6115H", "ELPC75" from Gun-ei Chemical Co., Ltd.

[0129] As the active ester curing agent, a compound having one or more active ester groups in one molecule can be used. Among these, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferred as the active ester curing agent. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent derived from a carboxylic acid compound is preferred, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is more preferred, and an active ester curing agent obtained from a carboxylic acid compound and an aromatic hydroxy compound is even more preferred.

[0130] As the carboxylic acid compound, either an aromatic carboxylic acid compound or an aliphatic carboxylic acid compound may be used. Examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and halogens thereof.

[0131] Examples of aromatic hydroxy compounds include (i) polyaddition products of unsaturated aliphatic cyclic compounds containing two double bonds in one molecule and phenols, (ii) various bisphenol compounds, (iii) aromatic polyols in which two or more hydroxyl groups are bonded to a carbon atom on an aromatic ring, and (iv) aromatic monools in which one hydroxyl group is bonded to a carbon atom on an aromatic ring. Examples of polyaddition products of unsaturated aliphatic cyclic compounds and phenols include polyaddition products of unsaturated aliphatic cyclic compounds such as dicyclopentadiene, tetrahydroindene, norbornadiene, limonene, and vinylcyclohexene with phenols that may have substituents (e.g., phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, etc.), and specifically, for example, dicyclopentadiene-phenol polyadditions. Examples of bisphenol compounds include bisphenol A, bisphenol F, bisphenol AF, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, and bisphenol M. Examples of aromatic polyols, in which two or more hydroxyl groups are bonded to a carbon atom on an aromatic ring, include hydroquinone, resorcinol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and phenol novolac. Examples of aromatic monools, in which one hydroxyl group is bonded to a carbon atom on an aromatic ring, include phenol, cresol, xylenol, ethylphenol, propylphenol, vinylphenol, allylphenol, phenylphenol, benzylphenol, halophenol, naphthol, methylnaphthol, dimethylnaphthol, ethylnaphthol, propylnaphthol, vinylnaphthol, allylnaphthol, phenylnaphthol, benzylnaphthol, and halonaphthol.

[0132] Specific examples of active ester resins include active ester resins containing a dicyclopentadiene-type diphenol structure, active ester resins containing a naphthalene structure, active ester resins containing acetylated phenol novolacs, and active ester resins containing benzoylated phenol novolacs. Commercially available active ester curing agents include, as active ester resins containing a dicyclopentadiene-type diphenol structure, "EXB-9451", "EXB-9460", "EXB-9460S", "HPC-8000-65T", "HPC-8000H-65TM", and "HPC-8000L-65TM" (manufactured by DIC Corporation); and as active ester resins containing a naphthalene structure, "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "HP-B-81 Examples include "51-62T", "HP-C-8151-62T", and "EXB-8150L-65T" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester resin; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester resin that is an acetylated phenol novolac; "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester resins that are benzoylated phenol novolacs; and "PC1300-02-65MA" (manufactured by Air Water Corporation) as an active ester resin containing a styryl group and a naphthalene structure.

[0133] The active ester-based curing agent preferably contains an ethylenically unsaturated bond-containing group. The ethylenically unsaturated bond-containing group is preferably an optionally substituted alkenyl group, an optionally substituted alkenylaryl group, or an optionally substituted arylalkenyl group. From the viewpoint of better enjoying the effects of the present invention, the number of carbon atoms in the alkenyl group is preferably 2 or more or 3 or more, with an upper limit preferably 10 or less, more preferably 8 or less, 6 or less, or 4 or less. From the viewpoint of better enjoying the effects of the present invention, the number of carbon atoms in the arylalkenyl group or alkenylaryl group is preferably 8 or more, with an upper limit preferably 20 or less, more preferably 18 or less, 16 or less, 14 or less, or 12 or less. Furthermore, from the viewpoint of better enjoying the effects of the present invention, alkyl groups, alkoxy groups, aryl groups, or hydroxyl groups are preferred as substituents, with alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups having 6 to 14 carbon atoms, or hydroxyl groups being more preferred.

[0134] From the viewpoint of more fully enjoying the effects of the present invention, it is preferable that the active ester-based curing agent contains two or more ethylenically unsaturated bond-containing groups in its molecule. Furthermore, from the viewpoint of more fully enjoying the effects of the present invention, the ethylenically unsaturated bond equivalent of the active ester-based curing agent is preferably 500 g / eq. or less, more preferably 450 g / eq. or less, or 400 g / eq. or less, and the lower limit is preferably 150 g / eq. or more, more preferably 160 g / eq. or more, or 180 g / eq. or more.

[0135] As mentioned above, active ester curing agents can be synthesized by reacting a carboxylic acid compound with an aromatic hydroxy compound. However, active ester curing agents containing an ethylenically unsaturated bond can be synthesized using starting compounds that contain an ethylenically unsaturated bond. The aromatic monool that constitutes the molecular chain terminal structure of the active ester curing agent is an aromatic monool containing an ethylenically unsaturated bond, for example, a C2-C 10 Alkenylphenols (vinylphenol, allylphenol, etc.), C2-C10 It is preferable to synthesize using alkenyl naphthols (vinyl naphthol, allyl naphthol, etc.). Therefore, in one preferred embodiment, the active ester curing agent is an ethylenically unsaturated bond-containing group (preferably C2-C 10 Alkenyl-C6-C 14 The molecule contains an aryl group (preferably at the end of the molecular chain).

[0136] Specific examples of benzoxazine-based curing agents include "JBZ-OD100" (benzoxazine ring equivalent 218 g / eq.), "JBZ-OP100D" (benzoxazine ring equivalent 218 g / eq.), and "ODA-BOZ" (benzoxazine ring equivalent 218 g / eq.) manufactured by JFE Chemical Corporation; "Pd" (benzoxazine ring equivalent 217 g / eq.) and "Fa" (benzoxazine ring equivalent 217 g / eq.) manufactured by Shikoku Chemicals Corporation; and "HFB2006M" (benzoxazine ring equivalent 432 g / eq.) manufactured by Showa Polymer Co., Ltd.

[0137] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl) thioether, and bis(4-cyanatephenyl) ether; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc.; and prepolymers in which these cyanate resins are partially triazined. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (phenol novolac type polyfunctional cyanate ester resins) from arxada, "ULL-950S" (polyfunctional cyanate ester resin), "BA230", and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate is triazined and trimerized).

[0138] Specific examples of carbodiimide-based curing agents include Carbodilite® V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemical Corporation, and Stavaxol® P (carbodiimide group equivalent: 302 g / eq.) manufactured by Lanxess.

[0139] When the resin composition of the present invention contains a curing agent (F), the content of component (F) in the resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, 25% by mass or more, or 30% by mass or more, when the total resin components in the resin composition are considered as 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. The upper limit of the curing agent content is preferably 70% by mass or less, more preferably 65% ​​by mass or less, 60% by mass or less, or 55% by mass or less.

[0140] When the resin composition of the present invention contains a curing agent (F), the content of the curing agent (f1) is preferably 50% by mass or more, more preferably 60% by mass or more, 70% by mass or more, or 80% by mass or more, and there is no particular upper limit, and it may be 100% by mass.

[0141] <(G) Organic solvents> The resin composition of the present invention may further contain (G) an organic solvent as an optional volatile component. Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and ethers such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, and methyl methoxypropionate. Examples of solvents include ester ester solvents; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. Organic solvents may be used individually or in combination of two or more.

[0142] If the resin composition of the present invention contains (G) an organic solvent, the content of (G) the organic solvent in the resin composition may be determined according to the properties required for the resin composition, but when the total components in the resin composition are taken as 100% by mass, it may be, for example, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, etc.

[0143] <(H) Other additives>The resin composition of the present invention may further contain any additives. Examples of such additives include thermosetting resins other than epoxy resins such as benzocyclobutene resin, epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, polyimide resin, benzoxazine resin, unsaturated polyester resin, phenol resin, and melamine resin; radical polymerizable resins such as maleimide resin, (meth)acrylic resin, and styryl resin; radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, and polyester resin; organometallic compounds such as organocumeric compounds, organozinc compounds, and organocumeric compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; and vent Thickeners such as montmorillonite; defoamers such as silicone-based defoamers, acrylic-based defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion improvers such as triazole-based adhesion improvers, tetrazole-based adhesion improvers, and triazine-based adhesion improvers; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; phosphorus-based flame retardants (e.g., phosphate ester compounds) Examples of flame retardants include phosphazene compounds, phosphinic acid compounds, red phosphorus, nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic acid anhydride-based stabilizers.The content of such additives may be determined according to the properties required of the resin composition. Furthermore, components (A1), (A2), (A3), (B) to (G) may have functions other than epoxy resin, such as thermosetting resin, radical polymerizable resin, radical polymerization initiator, thermoplastic resin, organometallic compound, colorant, polymerization inhibitor, leveling agent, thickener, defoamer, ultraviolet absorber, adhesion enhancer, adhesion imparterant, antioxidant, fluorescent whitening agent, surfactant, flame retardant, dispersant, stabilizer, etc. In that case, such components shall be considered as components (A1), (A2), (A3), (B) to (G), rather than component (H).

[0144] <Method for producing resin compositions> The resin composition of the present invention can be manufactured by mixing the above-mentioned components (A1), (A2), (A3), (B), and (C) as essential components, and appropriately mixing the above-mentioned components (D) to (H) as optional components, and further by kneading or stirring using kneading means such as a three-roll mill, ball mill, bead mill, or sand mill, or stirring means such as a super mixer or planetary mixer, as needed.

[0145] Furthermore, the resin composition of the present invention may be prepared by mixing the above components (A1), (A2), (A3), (B), and (C) to prepare a resin composition (hereinafter, the resin composition prepared by mixing components (A1), (A2), (A3), (B), and (C) will be referred to as "Resin Composition 1"). Alternatively, components (D) to (H), which are optional components, may be added to Resin Composition 1 as needed to prepare a resin composition (hereinafter, the resin composition prepared by adding components (D) to (H) to Resin Composition 1 will be referred to as "Resin Composition 2"). Alternatively, components (D) to (H) may be added to Resin Composition 1 and used as is. In the present invention, "Resin Composition" encompasses both "Resin Composition 1" and "Resin Composition 2".

[0146] In one embodiment, the resin composition of the present invention has components (A1), (A2), and (A3) whose activity when reacting with a curing accelerator as a catalyst is adjusted to an appropriate range, thereby suppressing the curing reaction during storage of the resin composition. After preparing resin composition 1 by mixing components (A1), (A2), (A3), (B), and (C), and storing it for a certain period of time, components (D) to (H) can be added to prepare resin composition 2.

[0147] <Physical properties and applications of resin compositions> In one embodiment, the cured product of the resin composition of the present invention exhibits the characteristic of suppressed warping. When the amount of warping is measured in accordance with the Japan Electronics and Information Technology Industries Association (JEITA) standard JEITA EDX-7311-24, it is preferably 3000 μm or less, more preferably 2500 μm or less, even more preferably 2000 μm or less, and particularly preferably 1500 μm or less. There is no particular lower limit, but it can be 1 μm or more, 10 μm or more, etc. The amount of warping can be measured according to the method described in the examples below.

[0148] In one embodiment, the resin composition of the present invention exhibits excellent filling properties for gaps and spaces between electrodes. Specifically, when the resin composition of the present invention is compression-molded onto the central part of a silicon wafer using a compression molding apparatus, it is preferable that the resin reaches the mold size. Furthermore, it is preferable that there be one or fewer resin voids at the resin edges, and more preferably that there are no resin voids at all. The filling properties can be evaluated according to the methods described in the examples below.

[0149] In one embodiment, the cured product of the resin composition of the present invention exhibits high adhesion strength to a silicon wafer. The adhesion strength between the cured product and the silicon wafer after a high-temperature, high-humidity environment test (HAST) conducted under the conditions of 130°C, 85%RH, and 96 hours was 400 kgf / cm². 2 The above is preferable, and 500 kgf / cm² 2 The above is more preferable, 550 kgf / cm² 2 The above is even more preferable, 600 kgf / cm² 2The above is particularly preferable. There is no particular upper limit, but 2000 kgf / cm² is preferable. 2 The following are possible. The adhesion strength can be measured according to the method described in the examples below.

[0150] In one embodiment, the resin composition of the present invention exhibits excellent workability during compression molding. Specifically, when the resin composition of the present invention is compressed and molded on a silicon wafer using a compression molding apparatus to form a resin composition layer with a thickness of 700 μm, the release film provided on the mold is preferably peeled off manually from the resin composition layer, and more preferably peeled off automatically. The workability during compression molding can be evaluated according to the method described in the examples below.

[0151] In one embodiment, the resin composition of the present invention exhibits the characteristic of suppressing flow marks when heat-cured. When a resin composition molded body with a thickness of 300 μm is formed on a silicon wafer and the resin composition molded body is heat-cured by heating at 150°C for 60 minutes, the area occupied by flow marks on the entire surface of the resin composition layer is preferably less than 20%, more preferably less than 15%, and particularly preferably less than 10%. There is no particular lower limit, but it can be 0% or more, 0.1% or more, etc. Flow marks can be evaluated according to the method described in the examples below.

[0152] In one embodiment, the resin composition of the present invention exhibits the characteristic that when MUF (Mold Underfill) evaluation is performed, the resin fills the spaces between bumps and no voids or unfilled areas are observed. Furthermore, even when the resin composition of the present invention is stored for 2 hours or 12 hours after preparation, it exhibits the characteristic that the resin fills the spaces between bumps and no voids or unfilled areas are observed in MUF evaluation. MUF (Mold Underfill) evaluation can be performed according to the method described in the examples below.

[0153] The applications of the resin composition of the present invention are not particularly limited, but it can be suitably used as an insulating material with low transmission loss required for 5G applications and the like, as well as in various liquid compound products that require good fluidity, filling properties, and adhesion. For example, the resin composition of the present invention can be used as an insulating material, adhesive, casting material, fiber-reinforced composite material, encapsulant, underfill material, mold underfill material, etc. Furthermore, because the resin composition of the present invention exhibits good fluidity and filling properties, it can be easily molded using compression molding. Therefore, in a preferred embodiment, the resin composition of the present invention is for insulating, adhesive, casting material, fiber-reinforced composite material, encapsulant, underfill, or mold underfill, and it is more preferable to use it for encapsulant, insulating, or mold underfill.

[0154] In particular, from the viewpoint of enjoying the effects of the present invention, which can be enjoyed to the fullest extent, such as the simultaneous achievement of characteristics such as suppression of warping, filling ability into gaps and gaps between electrodes, adhesion, and suppression of flow marks, the resin composition of the present invention can be suitably used as an insulating material for electronic components such as semiconductor chip packages, printed wiring boards, and circuit boards (resin composition for insulating material of electronic components). For example, it can be suitably used as a resin composition for encapsulating semiconductor chips (resin composition for semiconductor encapsulation), a resin composition for filling the gap between a circuit board (substrate for semiconductor chip package) and a semiconductor chip (resin composition for underfill), a resin composition for filling the gap between a circuit board and a semiconductor chip and encapsulating a semiconductor chip (resin composition for mold underfill), a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), a resin composition for forming an insulating layer of a semiconductor chip package (resin composition for insulating layer of semiconductor chip package), and a resin composition for a redistribution forming layer as an insulating layer for forming a redistribution layer in a semiconductor chip package (resin composition for redistribution forming layer).

[0155] As described above, the resin composition of the present invention can also be used as a material for forming a sealing layer or insulating layer of a semiconductor chip package. Examples of semiconductor chip packages include FC-CSP, MIS-BGA package, ETS-BGA package, fan-out type WLP (Wafer Level Package), fan-in type WLP, fan-out type PLP (Panel Level Package), and fan-in type PLP.

[0156] By forming a sealing layer, a redistribution layer, etc., using the resin composition of the present invention, it is possible to realize a semiconductor chip package with extremely low transmission loss while suppressing the occurrence of flow marks and voids, regardless of whether the semiconductor chip package is a fan-in type package or a fan-out type package. In one embodiment, the semiconductor chip package of the present invention is a fan-out type package. The resin composition of the present invention can be applied to fan-out type panel-level packages (FOPLPs) and fan-out type wafer-level packages (FOWLPs). In one embodiment, the semiconductor chip package of the present invention is a fan-out type panel-level package (FOPLP). In another embodiment, the semiconductor chip package of the present invention is a fan-out type wafer-level package (FOWLP).

[0157] [Printed wiring board and method for manufacturing the same] The printed circuit board of the present invention includes an insulating layer formed by comprising a cured product of the resin composition of the present invention. This printed circuit board can be manufactured, for example, by a manufacturing method comprising the following steps (1) and (2). (1) A step of forming a resin composition layer containing the resin composition on a substrate by compression molding. (2) A step of forming an insulating layer by heat curing the resin composition layer.

[0158] The cured product of the resin composition described above may be used not only as a sealing layer for semiconductor chips on a circuit board, as described later, but also as an insulating layer included in the circuit board. However, the insulating layer may be formed from a material other than the cured product of the resin composition described above.

[0159] <Process (1)> In step (1), a substrate is prepared. Examples of substrates include glass epoxy substrates, metal substrates (such as stainless steel or cold-rolled steel sheet (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may also have a metal layer, such as copper foil, on its surface as part of the substrate. For example, a substrate having a peelable first metal layer and a second metal layer on both surfaces may be used. When such a substrate is used, a conductor layer, which functions as a wiring layer for circuit wiring, is usually formed on the side of the second metal layer opposite to the first metal layer. An example of a substrate having such a metal layer is "Micro Thin," an ultra-thin copper foil with carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd.

[0160] The surface area of ​​the base material is preferably 900 mm². 2 The above, more preferably 1000 mm 2 More preferably 1500mm 2 That's all. There is no particular upper limit, but 5000mm 2 The following are possible options.

[0161] Furthermore, a conductive layer may be formed on one or both surfaces of the substrate. In the following description, a component including the substrate and the conductive layer formed on the surface of the substrate may be appropriately referred to as a "substrate with wiring layer". Examples of conductive materials included in the conductive layer include materials containing one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. As the conductive material, a single metal may be used, or an alloy may be used. Examples of alloys include alloys of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoint of versatility in conductive layer formation, cost, and ease of patterning, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper as single metals; and nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy alloys as alloys; are preferred. Among these, single metals such as chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper; and nickel-chromium alloys are more preferred, with single metal copper being particularly preferred.

[0162] The conductor layer may be patterned, for example, to function as a wiring layer. In this case, the line (circuit width) / space (width between circuits) ratio of the conductor layer is not particularly limited, but is preferably 20 / 20 μm or less (i.e., pitch of 40 μm or less), more preferably 10 / 10 μm or less, even more preferably 5 / 5 μm or less, even more preferably 1 / 1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch does not need to be the same throughout the entire conductor layer. The minimum pitch of the conductor layer may be, for example, 40 μm or less, 36 μm or less, or 30 μm or less.

[0163] The thickness of the conductor layer depends on the design of the printed circuit board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, even more preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

[0164] The conductive layer can be formed by a method that includes, for example, the steps of laminating a dry film (photosensitive resist film) onto a substrate, forming a pattern by exposing and developing the dry film under predetermined conditions using a photomask to form a pattern dry film, forming a conductive layer by a plating method such as electroplating using the developed pattern dry film as a plating mask, and peeling off the pattern dry film. As the dry film, a photosensitive dry film made of a photoresist composition can be used, for example, a dry film made of a resin such as novolac resin or acrylic resin can be used. The lamination conditions between the substrate and the dry film may be the same as the lamination conditions between the substrate and the resin sheet described later. The dry film can be peeled off by using an alkaline peeling solution such as a sodium hydroxide solution.

[0165] After preparing the substrate, a resin composition layer is formed on the substrate. If a conductive layer is formed on the surface of the substrate, it is preferable to form the resin composition layer in such a way that the conductive layer is embedded in the resin composition layer.

[0166] The resin composition layer is formed by compression molding. Compression molding typically involves placing the substrate and resin composition in a mold and applying pressure and, if necessary, heat to the resin composition within the mold to form a resin composition layer on the substrate.

[0167] The specific operation of the compression molding method is carried out as follows: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is applied to the substrate. The substrate coated with the resin composition is attached to the lower mold. Then, the upper and lower molds are clamped together, and heat and pressure are applied to the resin composition to perform compression molding.

[0168] Furthermore, the specific operation of the compression molding method may be as follows, for example: An upper mold and a lower mold are prepared as molds for compression molding. The resin composition is placed on the lower mold. The base material is attached to the upper mold. Then, the upper and lower molds are clamped together so that the resin composition on the lower mold is in contact with the base material attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0169] The molding conditions vary depending on the composition of the resin composition. For example, the mold temperature during molding is preferably a temperature at which the resin composition exhibits excellent compression moldability, preferably 80°C or higher, more preferably 100°C or higher, particularly preferably 120°C or higher, preferably 200°C or lower, more preferably 170°C or lower, and particularly preferably 150°C or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or more, more preferably 2 minutes or more, particularly preferably 5 minutes or more, preferably 60 minutes or less, more preferably 30 minutes or less, and particularly preferably 20 minutes or lower. Typically, the mold is removed after the formation of the resin composition layer. The mold may be removed before or after the heat curing of the resin composition layer.

[0170] The compression molding method may also be performed by extruding the resin composition filled in the cartridge into the lower mold. The molding conditions after the formation of the resin composition layer are the same as those for compression molding.

[0171] In another embodiment of step (1), the resin composition layer may be formed, for example, by laminating a resin sheet and a substrate. This lamination can be performed, for example, by heat-pressing the resin sheet onto the substrate from the support side, thereby bonding the resin composition layer to the substrate. Examples of a member used to heat-press the resin sheet onto the substrate (hereinafter sometimes referred to as the "heat-pressing member") include a heated metal plate (such as a SUS end plate) or a metal roll (such as a SUS roll). It is preferable to press the resin sheet via an elastic material such as heat-resistant rubber, rather than directly pressing the heat-pressing member onto the resin sheet, so that the resin sheet can adequately follow the surface irregularities of the substrate.

[0172] Lamination of the substrate and the resin sheet may be carried out, for example, by a vacuum lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C. The heat-pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa. The heat-pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

[0173] After lamination, the laminated resin sheets may be smoothed by pressing a heat-sealing member from the support side under normal pressure (atmospheric pressure). The pressing conditions for the smoothing process can be the same as the heat-sealing conditions for lamination. Lamination and smoothing may be performed continuously using a vacuum laminator.

[0174] <Process (2)> In step (2), a resin composition layer is formed on the substrate, and then the resin composition layer is heat-cured to form an insulating layer. The heat-curing conditions for the resin composition layer vary depending on the type of resin composition, but the curing temperature is usually in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably in the range of 170°C to 200°C), and the curing time is in the range of 5 minutes to 180 minutes (preferably in the range of 10 minutes to 120 minutes, more preferably in the range of 15 minutes to 100 minutes).

[0175] Before thermal curing the resin composition layer, the resin composition layer may be subjected to a preheating treatment by heating it at a temperature lower than the curing temperature. For example, prior to thermal curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but less than 120°C (preferably 60°C or higher but 110°C or lower, more preferably 70°C or higher but 100°C or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

[0176] As described above, a printed circuit board having an insulating layer can be manufactured. Furthermore, the method for manufacturing a printed circuit board may include any additional steps. For example, when a printed circuit board is manufactured using a resin sheet, the method for manufacturing the printed circuit board may include a step of peeling off the support of the resin sheet. The support may be peeled off before the heat curing of the resin composition layer, or after the heat curing of the resin composition layer.

[0177] A method for manufacturing a printed circuit board may include, for example, a step of polishing the surface of an insulating layer after forming the insulating layer. The polishing method is not particularly limited. For example, the surface of the insulating layer can be polished using a surface grinding machine.

[0178] A method for manufacturing a printed circuit board may include, for example, a step of inter-layer connection of conductor layers (3) and a step of drilling holes in the so-called insulating layer (4). This allows for the formation of holes such as via holes and through holes in the insulating layer. Examples of methods for forming via holes include laser irradiation, etching, and mechanical drilling. The dimensions and shape of the via holes may be determined as appropriate according to the design of the circuit board. Step (3) may also involve inter-layer connection by polishing or grinding the insulating layer.

[0179] After the via holes are formed, it is preferable to perform a step to remove the smear inside the via holes. This step is sometimes called a desmear step. For example, when the conductive layer on the insulating layer is formed by a plating step, a wet desmear treatment may be performed on the via holes. Also, when the conductive layer on the insulating layer is formed by a sputtering step, a dry desmear step such as a plasma treatment step may be performed. Furthermore, the insulating layer may be roughened by the desmear step.

[0180] Furthermore, the insulating layer may be roughened before forming the conductive layer on the insulating layer. This roughening treatment typically roughens the surface of the insulating layer, including the areas within via holes. The roughening treatment may be either dry or wet. An example of a dry roughening treatment is plasma treatment. An example of a wet roughening treatment is a method in which swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution are performed in that order.

[0181] After forming via holes, a conductor layer is formed on the insulating layer. By forming the conductor layer at the location where the via holes were formed, the newly formed conductor layer and the conductor layer on the substrate surface become electrically connected, and interlayer connection is established. Examples of methods for forming the conductor layer include plating, sputtering, and vapor deposition, with plating being preferred. In a preferred embodiment, a conductor layer having a desired wiring pattern is formed by plating the surface of the insulating layer using an appropriate method such as a semi-additive method or a fully additive method. Furthermore, if the support in the resin sheet is a metal foil, a conductor layer having a desired wiring pattern can be formed by a subtractive method. The material of the formed conductor layer may be a single metal or an alloy. In addition, this conductor layer may have a single-layer structure or a multi-layer structure including two or more layers of different types of materials.

[0182] Here, an example of an embodiment for forming a conductor layer on an insulating layer will be described in detail. A plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer, exposing a portion of the plating seed layer in accordance with the desired wiring pattern. After forming an electroplated layer on the exposed plating seed layer by electroplating, the mask pattern is removed. Subsequently, the unnecessary plating seed layer can be removed by etching or other processes to form a conductor layer having the desired wiring pattern. The dry film used to form the mask pattern when forming the conductor layer is the same as the dry film described above.

[0183] A method for manufacturing a printed circuit board may include a step of removing a substrate. By removing the substrate, a printed circuit board having an insulating layer and a conductor layer embedded in the insulating layer is obtained. This step can be performed, for example, when using a substrate having a peelable metal layer.

[0184] [Semiconductor chip package and method for manufacturing the same] The semiconductor chip package according to the first embodiment of the present invention includes the printed circuit board described above and a semiconductor chip mounted on the printed circuit board. As described above, the printed circuit board of the present invention includes a cured product of the resin composition of the present invention, and therefore the semiconductor chip package according to the first embodiment of the present invention includes a cured product of the resin composition of the present invention. This semiconductor chip package can be manufactured by bonding a semiconductor chip to a printed circuit board.

[0185] The bonding conditions between the printed circuit board and the semiconductor chip can be any conditions that allow for conductive connection between the terminal electrodes of the semiconductor chip and the circuit wiring of the printed circuit board. For example, conditions used in flip-chip mounting of semiconductor chips can be adopted. Alternatively, for example, the semiconductor chip and the printed circuit board may be bonded via an insulating adhesive.

[0186] An example of a bonding method is a method of crimping a semiconductor chip onto a printed circuit board. The crimping conditions are typically a crimping temperature in the range of 120°C to 240°C (preferably in the range of 130°C to 200°C, more preferably in the range of 140°C to 180°C), and a crimping time in the range of 1 second to 60 seconds (preferably in the range of 5 seconds to 30 seconds).

[0187] Another example of a bonding method is to bond semiconductor chips to a printed circuit board by reflow soldering. The reflow conditions may be in the range of 120°C to 300°C.

[0188] After bonding the semiconductor chip to the printed circuit board, the semiconductor chip may be filled with mold underfill material. As this mold underfill material, the resin composition described above may be used, or the resin sheet described above may be used.

[0189] A semiconductor chip package according to a second embodiment of the present invention includes a semiconductor chip and a cured product of the resin composition that encapsulates the semiconductor chip. An example of a semiconductor chip package according to the second embodiment is a fan-out type WLP.

[0190] The manufacturing method for such semiconductor chip packages is (A) A step of laminating a temporary fixing film onto the substrate, (B) A step of temporarily fixing the semiconductor chip onto a temporary fixing film, (C-1) A step of forming a resin composition layer containing the resin composition of the present invention on a semiconductor chip by compression molding, (C-2) A step of heat curing the resin composition layer, (D) Steps to peel off the substrate and temporary fixing film from the semiconductor chip, (E) A step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off. (F) A step of forming a redistribution layer as a conductor layer on a redistribution formation layer, and (G) A step of forming a solder resist layer on the redistribution layer, Includes.

[0191] (Process (A)) Step (A) is a step of laminating a temporary fixing film onto the substrate. The lamination conditions between the substrate and the temporary fixing film may be the same as those for lamination between the substrate and the resin sheet in the manufacturing method of a circuit board.

[0192] Examples of substrates include silicon wafers, glass wafers, glass substrates, metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates, which are made by impregnating glass fibers with epoxy resin and then heat-curing them; and substrates made of bismaleimide triazine resin such as BT resin. The area of ​​the substrate is preferably the same as the area of ​​the substrate described in the above [Printed Wiring Board and Method for Manufacturing the Same].

[0193] The temporary fixing film can be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Examples of commercially available products include Nitto Denko's "Riva Alpha".

[0194] (Process (B)) Step (B) is a step of temporarily fixing the semiconductor chip onto a temporary fixing film. Temporary fixing of the semiconductor chip can be performed using equipment such as a flip-chip bonder or die bonder. The layout and number of semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor chip packages to be produced, etc. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and then temporarily fixed.

[0195] (Process (C-1) and Process (C-2)) Steps (C-1) and (C-2) (hereinafter, steps (C-1) and (C-2) may be collectively referred to as "step (C)") are steps for forming a sealing layer on a semiconductor chip. The sealing layer can be formed by a cured product of the resin composition of the present invention. The sealing layer is formed by a method including the steps of forming a resin composition layer on a semiconductor chip by compression molding and thermal curing of this resin composition layer to form a cured product layer as a sealing layer. The formation of the resin composition layer on a semiconductor chip can be carried out in the same way as the method for forming a resin composition layer on a substrate described in [Printed Wiring Board and Method for Manufacturing the Same], except that a semiconductor chip is used instead of a substrate.

[0196] After forming a resin composition layer on a semiconductor chip, this resin composition layer is heat-cured to obtain a sealing layer that covers the semiconductor chip. This seals the semiconductor chip with the cured resin composition of the present invention. The heat-curing conditions for the resin composition layer may be the same as those used in the manufacturing method of printed circuit boards. Furthermore, before heat-curing the resin composition layer, a preheating treatment may be performed on the resin composition layer, which is heated at a temperature lower than the curing temperature. The processing conditions for this preheating treatment may be the same as those used in the manufacturing method of printed circuit boards.

[0197] (Process (D)) Step (D) is a step of peeling the substrate and temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate peeling method depending on the material of the temporary fixing film. Examples of peeling methods include peeling by heating, foaming, or expanding the temporary fixing film. Another example of a peeling method is peeling by irradiating the temporary fixing film with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film and then peeling it off.

[0198] In the method of peeling off a temporary fixing film by heating, foaming, or expanding it, the heating conditions are typically 100°C to 250°C for 1 to 90 seconds or 5 to 15 minutes. In the method of peeling off a temporary fixing film by reducing its adhesive strength by irradiating it with ultraviolet light, the amount of ultraviolet light irradiated is typically 10 mJ / cm². 2 ~1000 mJ / cm 2 That is the case.

[0199] (Process (E)) Step (E) is a step of forming a rewiring layer as an insulating layer on the surface from which the substrate and temporary fixing film of the semiconductor chip have been peeled off. The rewiring layer can be formed in the same way as the method for forming a resin composition layer on a substrate described in [Printed Wiring Board and Method for Manufacturing the Same].

[0200] The material for the rewiring layer may be the resin composition of the present invention. In this case, the rewiring layer is preferably formed by compression molding.

[0201] After forming the redistribution layer, via holes may be formed in the redistribution layer to connect the semiconductor chip and the redistribution layer.

[0202] Methods for forming via holes include, for example, laser irradiation, etching, and mechanical drilling. Among these, laser irradiation is preferred. Laser irradiation can be performed using an appropriate laser processing machine that uses a light source such as a carbon dioxide laser, UV-YAG laser, or excimer laser.

[0203] The shape of the via hole is not particularly limited, but is generally circular (or nearly circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, preferably 3 μm or more, preferably 10 μm or more, and more preferably 15 μm or more. Here, the top diameter of the via hole refers to the diameter of the via hole opening on the surface of the redistribution forming layer.

[0204] (Process (F)) Step (F) is the step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer may be the same as the method of forming a conductor layer on an insulating layer in the manufacturing method of a circuit board. Alternatively, steps (E) and (F) may be repeated to alternately stack the redistribution layer and the redistribution formation layer (build-up).

[0205] (Process (G)) Step (G) is the step of forming a solder resist layer on the redistribution layer. Any insulating material can be used for the solder resist layer. Among these, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing semiconductor chip packages. Furthermore, the resin composition of the present invention may be used as the thermosetting resin.

[0206] Furthermore, in step (G), bumping may be performed to form bumps as needed. Bumping can be carried out by methods such as solder balls or solder plating. The formation of via holes in the bumping process can be carried out in the same manner as in step (E).

[0207] In addition to steps (A) to (G), the method for manufacturing a semiconductor chip package may also include step (H), which involves dicing a plurality of semiconductor chip packages into individual semiconductor chip packages. Step (H) is the process of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages. The method for dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited and can be carried out by known methods.

[0208] [Semiconductor device] Examples of semiconductor devices on which the above-described semiconductor chip package is mounted include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft, etc.). As described above, the semiconductor chip package of the present invention includes a cured product of the resin composition of the present invention, and therefore the semiconductor device of the present invention includes a cured product of the resin composition of the present invention. [Examples]

[0209] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass," respectively.

[0210] <Example 1> (A1) Component: 8 parts of polypropylene oxy-modified bisphenol A type epoxy resin (ADEKA "EP-4000L", epoxy equivalent approximately 255 g / eq.), (A2) Component: 8 parts of glycidylamine type epoxy resin (ADEKA "EP-3950L", epoxy equivalent 95 g / eq.), (A2) Component: 3 parts of bisphenol A type epoxy resin (DIC "EXA-850CRP", epoxy equivalent 172 g / eq.), (B) Component: imidazole-based curing accelerator (Shikoku Chemicals, Inc. "2E4MZ-CN" (1-(2-cyanoethyl)-2-ethyl-4-methylimidazole)), (C) Component: inorganic filler (1) (average particle size: 1.5 μm, specific surface area: 4.9 m²) 2 Resin composition 1 was prepared by uniformly dispersing 90 parts of spherical silica (N-phenyl-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., with a maximum cut diameter of 3 μm) using a mixer.

[0211] To the obtained resin composition 1, 0.5 parts of a compound having a polysiloxane structure and a polyalkylene oxy structure (Shin-Etsu Chemical Co., Ltd. "KF-1002") as component (D), 0.1 parts of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-403" (3-glycidoxypropyltrimethoxysilane)) as component (E), and 0.1 parts of a silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane)) as component (E) were added and uniformly dispersed using a mixer to prepare resin composition 2.

[0212] <Example 2> Resin composition 1 was prepared in the same manner as in Example 1, except that 0.5 parts of the imidazole-based curing accelerator (2E4MZ-CN, manufactured by Shikoku Chemicals, Inc.) was replaced with 0.5 parts of the imidazole-based curing accelerator (C11Z-CN, manufactured by Shikoku Chemicals, Inc. (1-(2-cyanoethyl)-2-undecylimidazole)). Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0213] <Example 3> 90 parts of inorganic filler (1) from Example 1 were mixed with inorganic filler (2) (average particle size: 0.5 μm, specific surface area: 10 m²). 2 Resin composition 1 was prepared in the same manner as in Example 1, except that 80 parts of spherical silica treated with "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ( / g, maximum cut diameter: 5 μm) were used. Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0214] <Example 4> Resin composition 1 was prepared in the same manner as in Example 1, except that the amount of polypropylene oxy-modified bisphenol A type epoxy resin (ADEKA "EP-4000L") added was changed from 8 parts to 3 parts, the amount of bisphenol A type epoxy resin (DIC "EXA-850CRP") added was changed from 3 parts to 8 parts, and 90 parts of inorganic filler (1) was changed to 80 parts of inorganic filler (2). Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0215] <Example 5> Resin composition 1 was prepared in the same manner as in Example 2. Using the obtained resin composition 1, resin composition 2 was prepared in the same manner as in Example 2, except that the amount of compound having a polysiloxane structure and a polyalkylene oxy structure (KF-1002, manufactured by Shin-Etsu Chemical Co., Ltd.) added was changed from 0.5 parts to 2 parts.

[0216] <Example 6> Resin composition 1 was prepared in the same manner as in Example 2. Using the obtained resin composition 1, resin composition 2 was prepared in the same manner as in Example 2, except that the compound having a polysiloxane structure and a polyalkylene oxy structure (KF-1002, manufactured by Shin-Etsu Chemical Co., Ltd.) was not added.

[0217] <Example 7> Resin composition 1 was prepared in the same manner as in Example 1, except that the amount of glycidylamine-type epoxy resin (ADEKA "EP-3950L") added was changed from 8 parts to 6 parts, 3 parts of bisphenol A-type epoxy resin (DIC "EXA-850CRP") were omitted, 6 parts of dicyclopentadiene-type epoxy resin (ADEKA "EP-4088S", epoxy equivalent 170 g / eq.) were added as component (A3), and 90 parts of inorganic filler (1) were changed to 80 parts of inorganic filler (2). Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0218] <Example 8> Resin composition 1 was prepared in the same manner as in Example 1, except that 8 parts of the glycidylamine type epoxy resin (ADEKA "EP-3950L") in Example 1 were replaced with 6 parts of naphthalene type epoxy resin (DIC "HP4032D", epoxy equivalent 142 g / eq.), and the amount of bisphenol A type epoxy resin (DIC "EXA-850CRP") added was changed from 3 parts to 6 parts. Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0219] <Example 9> Resin composition 1 was prepared in the same manner as in Example 4, except that 0.5 parts of the imidazole-based curing accelerator (2E4MZ-CN, manufactured by Shikoku Chemicals, Inc.) was replaced with 0.5 parts of an imidazole-based curing accelerator (2E4MZ (2-ethyl-4-methylimidazole), manufactured by Shikoku Chemicals, Inc.). Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 4.

[0220] <Example 10> Resin composition 1 was prepared in the same manner as in Example 1. Using the obtained resin composition 1, resin composition 2 was prepared in the same manner as in Example 1, except that 0.5 parts of the compound having a polysiloxane structure and a polyalkylene oxy structure (Shin-Etsu Chemical Co., Ltd. "KF-1002") in Example 1 was replaced with 0.5 parts of a silicone compound having a polydimethylsiloxane skeleton as the main chain and not having a polyalkylene oxy structure (Shin-Etsu Chemical Co., Ltd. "X-22-162C").

[0221] <Comparative Example 1> Resin composition 1 was prepared in the same manner as in Example 1, except that the amount of polypropylene oxy-modified bisphenol A type epoxy resin (ADEKA "EP-4000L") added was changed from 8 parts to 1.5 parts, and the amount of bisphenol A type epoxy resin (DIC "EXA-850CRP") added was changed from 3 parts to 9.5 parts. Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0222] <Comparative Example 2> Resin composition 1 was prepared in the same manner as in Example 1, except that the amount of polypropylene oxy-modified bisphenol A type epoxy resin (ADEKA "EP-4000L") added was changed from 8 parts to 15 parts, the amount of glycidylamine type epoxy resin (ADEKA "EP-3950L") added was changed from 8 parts to 2 parts, and the amount of bisphenol A type epoxy resin (DIC "EXA-850CRP") added was changed from 3 parts to 2 parts. Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 1.

[0223] <Comparative Example 3> Resin composition 1 was prepared in the same manner as in Example 2, except that the polypropylene oxy-modified bisphenol A type epoxy resin (ADEKA "EP-4000L") was not added, the amount of glycidylamine type epoxy resin (ADEKA "EP-3950L") added was changed from 8 parts to 10 parts, and the amount of bisphenol A type epoxy resin (DIC "EXA-850CRP") added was changed from 3 parts to 9 parts. Resin composition 2 was prepared using the obtained resin composition 1 in the same manner as in Example 2.

[0224] <Flow Mark Evaluation> Using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes), the resin compositions 2 prepared in Examples 1-10 and Comparative Examples 1-3 were compression molded on a 12-inch disc-shaped silicon wafer (thickness 775 μm). This formed a resin composition molded body with a thickness of 300 μm on the silicon wafer. Subsequently, the resin composition molded body was heat-cured by heating at 150°C for 60 minutes, and flow mark evaluation was performed according to the following criteria. The results are shown in Table 1. "○": Flow marks occupy less than 20% of the total surface area of ​​the resin composition layer. "×": Flow marks occupy 20% or more of the total surface area of ​​the resin composition layer.

[0225] <Warping evaluation> A 300 μm thick resin composition layer was formed on a 12-inch silicon wafer by compression molding of the resin compositions 2 prepared in Examples 1-10 and Comparative Examples 1-3 using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). The resin composition layer was then heat-cured by heating at 180°C for 90 minutes. This yielded a sample substrate containing the silicon wafer and the cured resin composition layer. The warpage of the sample substrate at 25°C was measured using a shadow moiré measuring device (Akorometrix "ThermoireAXP"). The measurement was performed in accordance with the Japan Electronics and Information Technology Industries Association (JEITA) standard JEITA EDX-7311-24. Specifically, a virtual plane calculated by the least squares method of all data on the substrate surface of the measurement area was used as the reference plane. The difference between the minimum and maximum values ​​in the perpendicular direction from this reference plane was determined as the warpage, and evaluated according to the following criteria. The results are shown in Table 1. "○": Curvature less than 2000 μm "△": Curvature of 2000 μm or more, and less than 2500 μm. "×": Curvature of 2500 μm or more

[0226] <Evaluation of workability during compression molding> On a 12-inch silicon wafer, the resin compositions prepared in Examples 1-10 and Comparative Examples 1-3 were compression molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 15 minutes) to form a resin composition layer with a thickness of 700 μm. The release film used on the mold during compression molding was AGC's "Aflex 50MW 390NT" and was evaluated according to the following criteria. "○": After compression molding, the release film automatically peels off from the resin composition layer. "△": The release film does not automatically peel off from the resin composition layer after compression molding, but it can be peeled off manually. "×": After compression molding, the release film adheres strongly to the resin composition layer and cannot be peeled off even by hand.

[0227] <Filling performance evaluation> 40 g of resin composition 2 prepared in Examples 1-10 and Comparative Examples 1-3 was supplied to the center of a 12-inch silicon wafer and compressed using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes). The resin reached the mold on the 12-inch silicon wafer, and the presence or absence of resin leakage at the resin edges after compression molding was checked and evaluated according to the following criteria. The results are shown in Table 1. "○": The resin has reached the mold size, and there is no resin leakage at the edges of the resin. "△": The resin has reached the mold size, but there is one spot where the resin has leaked out at the edge. "×": The resin has not reached the mold size, or there are multiple resin leaks at the edges of the resin.

[0228] <Adhesion to silicon wafers> On a 12-inch silicon wafer, the resin compositions 2 prepared in Examples 1-10 and Comparative Examples 1-3 were compression molded using a compression molding apparatus (mold temperature: 130°C, pressure: 6 MPa, curing time: 10 minutes) to form a resin composition layer with a thickness of 300 μm. The resin composition layer was then heat-cured by heating at 180°C for 90 minutes. This yielded a sample substrate containing the silicon wafer and the cured resin composition layer. Subsequently, a high-temperature, high-humidity environment test (HAST) was performed under the conditions of 130°C, 85% RH, and 96 hours. After the HAST test, the cured layer was polished using #180 sandpaper until the cured layer was 50 μm thick. The polished sample was cut into 1 cm square test pieces, and a φ2.7 mm adhesive stud pin was placed perpendicular to the cured layer. The sample was then heated at 150°C for 60 minutes to create a test piece in which the stud pin and the cured layer were bonded. The obtained stud pin-attached test specimens were subjected to vertical tensile testing using a QUAD GROUP "ROMULUS" vertical tensile testing machine at a test speed of 0.1 kg / sec. Measurements were taken for five test specimens, the average adhesion strength was calculated, and the results were evaluated according to the following criteria. The results are shown in Table 1. "○": Adhesion strength of 500 kgf / cm 2 That's all. "△": Adhesion strength of 400 kgf / cm 2Above, 500 kgf / cm 2 Less than "×": The adhesion strength is less than 400 kgf / cm 2 Less than

[0229] <Mold Underfill (MUF) Evaluation> On a 12-inch glass wafer with a thickness of 775 μm, a chip component with copper bumps (chip size: 10 mm × 10 mm, chip thickness: 300 μm, copper bump size diameter: 20 μm, height: 30 μm, copper bump pitch: 40 μm, "WALTS-TEG FBW40A-0001JY" manufactured by Waltz) was mounted on the glass wafer at the four corners using an adhesive so that the copper bumps were in contact. Resin compositions 2 prepared in Examples 1 to 10 and Comparative Examples 1 to 3, those stored at 25°C for 2 hours and 12 hours after preparation were used, and compression molding was performed using a compression molding device (mold temperature: 130°C, pressure: 6 MPa, cure time: 10 minutes) so that the resin thickness became 400 μm, thereby performing mold underfill (MUF) on the chip component. After the resin composition was subjected to a heat curing treatment at 150°C for 60 minutes, the presence or absence of voids was observed with a microscope from the back side of the glass wafer and evaluated according to the following criteria. The results are shown in Table 1. "○": The resin was filled between the bumps, and no voids or unfilled parts were observed. "×": There was a part where the resin was not filled between the bumps, and voids and unfilled parts were observed.

[0230]

Table 1

[0231] The abbreviations in the table are as follows. (Component (A1)) · EP-4000L: Polypropyleneoxy-modified bisphenol A type epoxy resin ("EP-4000L" manufactured by ADEKA, epoxy equivalent: about 255 g / eq.)

Chemical formula

[0232] (A2) Component • EP-3950L: Glycidylamine-type epoxy resin with an aromatic skeleton (ADEKA Corporation's "EP-3950L", epoxy equivalent 95g / eq.) • HP4032D: Naphthalene-type epoxy resin (DIC Corporation's "HP4032D", epoxy equivalent 142 g / eq.) • EXA-850CRP: Bisphenol A type epoxy resin (DIC Corporation's "EXA-850CRP", epoxy equivalent 172 g / eq.)

[0233] (A3) Ingredients • EP-4088S: Dicyclopentadiene type epoxy resin (ADEKA Corporation's "EP-4088S", epoxy equivalent 170g / eq.)

[0234] (B) Component • 2E4MZ-CN: Imidazole-based curing accelerator (Shikoku Chemicals Co., Ltd. "2E4MZ-CN" (1-(2-cyanoethyl)-2-ethyl-4-methylimidazole)) [ka] • C11Z-CN: Imidazole-based curing accelerator (Shikoku Chemicals Co., Ltd. "C11Z-CN" (1-(2-cyanoethyl)-2-undecylimidazole)) [ka] • 2E4MZ: Imidazole-based curing accelerator (Shikoku Chemicals Co., Ltd.'s "2E4MZ" (2-ethyl-4-methylimidazole))

[0235] (C) Component ·Inorganic filler (1): Average particle size: 1.5μm, specific surface area: 4.9m 2 Spherical silica treated with Shin-Etsu Chemical Co., Ltd.'s "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), with a maximum cut diameter of 3 μm per g. ·Inorganic filler (2): Average particle size: 0.5μm, specific surface area: 10m 2Spherical silica treated with Shin-Etsu Chemical Co., Ltd.'s "KBM-573" (N-phenyl-3-aminopropyltrimethoxysilane), with a maximum cut diameter of 5 μm per g.

[0236] (D) Component • X-22-162C: A silicone compound whose main chain is a polydimethylsiloxane skeleton and does not have a polyalkylene oxy structure (Shin-Etsu Chemical Co., Ltd. "X-22-162C", number average molecular weight: 4,600, liquid at 25°C) • KF-1002: A compound having a polysiloxane structure and a polyalkylene oxy structure (Shin-Etsu Chemical Co., Ltd.'s "KF-1002" (polyoxyethylene-methylpolysiloxane copolymer), number average molecular weight: approximately 4,300, liquid at 25°C)

[0237] (E) Component • KBM-403: Silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-403" (3-glycidoxypropyltrimethoxysilane)) • KBM-803: Silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM-803" (3-mercaptopropyltrimethoxysilane))

[0238] As shown in Table 1, Examples 1 to 10, which contained components (A1), (A2), (B), and (C) and whose mass ratio [(A1) component / (A2) component] was within the range specified in this application, exhibited small warpage and excellent filling properties and adhesion to the silicon chip. On the other hand, Comparative Example 2, in which the mass ratio [(A1) component / (A2) component] was greater than the range specified in this application, did not exhibit satisfactory filling properties or adhesion to the silicon chip. Furthermore, Comparative Example 1, in which the mass ratio [(A1) component / (A2) component] was smaller than the range specified in this application, and Comparative Example 3, which did not contain component (A1), resulted in large warpage.

Claims

1. (A1) Epoxy resin represented by the following formula (a-3), (A2) Liquid epoxy resin having an aromatic skeleton, (B) Curing accelerator, and (C) inorganic filler, A resin composition containing, A resin composition in which the mass ratio of component (A1) to component (A2) [component (A1) / component (A2)] is 0.1 to 3.

5. 【Chemistry 1】 (In the formula, Each Ar ring independently represents an aromatic carbon ring having 6 to 10 carbon atoms, which may have substituents selected from alkyl groups having 1 to 10 carbon atoms and aryl groups having 1 to 10 carbon atoms. X represents an alkylene group with 1 to 20 carbon atoms. Each Y independently represents an alkylene group with 1 to 10 carbon atoms. m1 and m2 each independently represent integers between 0 and 20, and at least one of m1 and m2 is 1 or greater. * indicates a bonding operation.

2. In formula (a-3), X is an alkylene group having 1 to 5 carbon atoms. Each Y is independently an alkylene group with 2 to 4 carbon atoms. The resin composition according to claim 1, wherein each Ar ring is an aromatic carbon ring having 6 to 10 carbon atoms, which may each independently have substituents selected from alkyl groups having 1 to 10 carbon atoms.

3. The resin composition according to claim 1, wherein component (B) is an imidazole-based curing accelerator having a cyano group.

4. The resin composition according to claim 1, wherein component (B) is 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole or 1-(2-cyanoethyl)-2-undecylimidazole.

5. The resin composition according to claim 1, further comprising an epoxy resin that does not fall under either component (A1) or component (A2) (hereinafter referred to as "component (A3)"), wherein component (A3) comprises a liquid epoxy resin.

6. Furthermore, the resin composition according to claim 1, comprising a polymer (hereinafter referred to as "component (D)") that satisfies the following conditions (d1) to (d3). Condition (d1): The number-average molecular weight is between 1,000 and 150,000. Condition (d2): Liquid at 25°C, or glass transition temperature is 25°C or lower. Condition (d3): Has a polysiloxane structure.

7. The resin composition according to claim 6, wherein component (D) is a polymer that further satisfies the following condition (d4). Condition (d4): Has a polyalkylene oxy structure.

8. The resin composition according to claim 1, wherein the mass ratio of component (B) to component (A1) [component (B) / component (A1)] is 0.001 to 1.

9. The resin composition according to claim 6, wherein the mass ratio of component (D) to component (A1) [component (D) / component (A1)] is 0.001 to 1.

10. The resin composition according to claim 1, wherein the total content of component (A1) and component (A2) is 5 to 50% by mass, when the nonvolatile components of the resin composition are considered to be 100% by mass.

11. The resin composition according to claim 1, wherein the content of component (A1) is 2 to 30% by mass, when the nonvolatile components of the resin composition are taken as 100% by mass.

12. The resin composition according to claim 1, wherein the content of component (C) is 50 to 90% by mass, when the non-volatile components of the resin composition are taken as 100% by mass.

13. A cured product of the resin composition according to any one of claims 1 to 12.

14. A semiconductor chip package comprising a cured product of the resin composition according to any one of claims 1 to 12.

15. The semiconductor chip package according to claim 14, which is a fan-out type package.

16. A semiconductor device comprising a cured product of the resin composition according to any one of claims 1 to 12.

17. A step of forming a resin composition layer containing the resin composition described in any one of claims 1 to 12 on a semiconductor chip by compression molding, and A step of thermally curing the resin composition layer, A method for manufacturing semiconductor chip packages, including [the specified component].

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